Water repellent composition



Patented Apr. 14, 1953 WATER REPELLENT COMPOSITION Hans G. Figdcr,Philadelphia, .Pa.

NoDrawing. Application July 8, 1948, Serial No. 37,535

16 Claims.

Thepresent'invention relates to treatment of fabrics-andit'particularlyrelates to water-repellent treatment of fabrics.

Although the present invention will be particularly directed to thetreatment of textile fiberspyarns and woven or knitted materials to givethem water repellency, the invention also has broader application totreatment of many diiferent types of material to give themwaterrepellent properties, such as paper, sheet material of variouscharacters, various types of surfaces or walls, etc.

The present invention will also be particularly described in connectionwith water-repellent compositions in which a wax or wax-like material,is combined with a polyvalent metal salt, and in which such emulsionsare stabilized to prevent aprecipitate from forming, as for example withan anionic surface active agent such assoap as the emulsifying 'agent.Where soap was employed protective colloids primarily consisting ofwater soluble protein were also required, such protein material, forexample, taking the form of glue or gelatin.

Such protective colloid, whether glue or gelatin,'was designed toprevent or to disperse the precipitate which would normally be formed asa result of the combination of the soap used as an emulsifier and thepolyvalent metal salt. However, even in this instance, although anapparently homogeneous heavy paste might result by blending the wax, thepolyvalent metal salt, othesoap and the protective colloid with vigorousagitation, upon dilution the stability would decrease.

Moreover, theemulsion orhea-vy paste would be quite thick and notreadily flowable, as is desirable, nor would it be stable on storage,and itwould tend to lose its ability to be diluted with water. Moreover,it would tend to acquire a putrid odor and render the goods to which itwas*appliedtreadilysubject to attack by mildew. At high temperature toothere would be a complete breakdown of the emulsion after arelativelyshortperi-od of time.

It-"was rnotjfound readily possible-to use more stable types :ofcolloids such as polyvinyl alcohol or methyl cellulose. These lastmentioned :protectivepolloids had the tendency of thickening anddecreasing the flowability of emulsion :and moreover :after applicationand drying on the'textile tstill' tended to retain their water dis-.persibility which decreased the .water repellency "of :the coating.

oOn .the other hand, where cationic emulsifyhandled, stored or shippedwith varying climatic conditions over extended periods without loss ofstrength or its desirable properties and without premature precipitationor decomposition which will avoid the above objectionablecharacteristics.

Another object is to provide a novel-waterrepellent treatment fortextile fabrics and other materials which will give water repellency ofmuch greater efiectiveness and of more durability without substantialincrease in the amountof wax or other water-repellent solid which .mustbe employed and without the need for using protective colloids, such asglue, gelatin, polyvinyl alcohol or methyl cellulose.

Another object is to provide a novel waterrepellent composition andwater-repellent treatment which will altogether eliminate the necessityof utilizing protective colloids giving riseto objectionable odors andtending to putrefy upon storage, and likely to render the water-proofedfabric readily attacked by mildew and other microorganisms, and whichmost objectionably may tend to decrease the tensile strength of fabricmaterials.

A further object of the present invention is to provide'a stable waxemulsion containing an aluminum or zirconium salt, which emulsion isthin and pourable, stable on storage, does not putrefy, and may bereadily diluted at the time of its use without breakdown and withoutprecipitation of wax particles and which may be stored indefinitely atelevated temperatures without loss of stability.

A still further object of the inventionis to provide a textile treatingprocess by which Itextile fibers, fabrics, yarns and similar materialsmay be rendered water-repellent with an.emulsion of a wax and analuminum or zirconium salt, without rendering the materialssusceptibleto attack by micro-organisms, without imparting to the materialsobjectionable :odor insstanding and without decreasing their tensilestrength-Jon storage.

It has Jaeen found that the: above objects may be most satisfactorilyaccomplished where small amounts of synthetic, non-soap, non-ionicemulsifying agents are added to or combined with a wax, a water solublepolyvalent metal salt and an anionic surface active agent.

The most satisfactory composition consists of a combination of wax, soapas an anionic agent, a solution of a water soluble polyvalent metal saltand a non-ionic surface-active agent of the synthetic type.

The wax employed in preparing the emulsion may be a mineral, vegetable,or animal wax, having a melting point above room temperature. It ispreferably hard and of amorphous, crystalline or microcrystallinestructure at room temperature.

Unctuous materials, like lanolin or petrolatum-although sometimesclassified as waxesare preferably not employed. I

Examples of suitable waxes are:

Paraffln Beeswax Carnauba wax Candelilla wax Ouricury wax Mixtures oftwo or more waxes may be employed if desired. Paraflin wax of a meltingpoint between 50 and 60 C. is preferred.

The anionic agent is desirably an alkali metal, ammonium, or organicamine soap. Amine soaps are preferred because they decompose on thefiber, increasing in this way the hydrophobic properties. Ammonium soapsare usually not preferred since they are less stable and more difflcultto control, on account of the greater volatility.

The amine component of the soap may be a primary, secondary or tertiaryamine, a polyamine, or a substituted amine, such as a hydroxyamine.Examples of such products are:

Methylamine Dimethylamine Trimethylamine Butylamine EthylenediamineMorpholine Monoethanolamine Diethanolamine TriethanolamineIsopropanolamine Hydroxyethyl-ethylenediamine Diethylamino-ethanol2-ethyl-2-amino-l-propanol 2-methyl-2-amino-1-3-propanediol Laurie acid'Myristic acid Palmitic acid Stearic acid Arachidic acid Behenic acidMixtures of such fatty acids may be employed, such as the fatty acidsfrom fish oil which have been hydrogenated to a very low iodine number.

*For the purpose of this invention, it is'not necessary to prepare theanionic agent separately. The anionic agent may also be formed in situ,by adding the amine to the water phase, melting the fatty acid togetherwith the wax, and combining the two phases at a temperature above themelting point of the wax and the fatty acid.

The polyvalent metal salt may be a water soluble salt of any metal ofgroup II to group VIII in'the periodic table of elements, with a shortchain, volatile organic acid, like formic or acetic acid. The salts ofaluminum and zirconium are preferred.

The non-ionic surface-active agents used in the emulsion should be waterdispersible. They may be:

(a) polyvalent alcohols and their anhydrides partly esterified with along chain carboxylic acid, containing at least 12 carbon atoms, such asmannitan monopalmitate, sorbitan monomyristate;

(b) or an ethylene oxide addition compound of such a product,containing, for example, 15 or more recurring CHQCHZO units to form apoly; oxy-ethylene ether;

(c) or a condensation product of an alkylphenol with ethylene oxide,such as the reaction product of iso-octylphenol with 6, or more,CHaCI-IzO units to form polyoxy-ethylene ethers of the formulaR-CeI-Li-O(CH2CH2O)1*H, in which R is an alkyl and a': is an integer, e.g. 6 or more;

(01) or a condensation product of alkyl-thiophenol with 10 to 15ethylene oxideunits forming a polyoxy-ethylene ether of the formulaa-cem-s- (01120320) 11H in which R. is an alkyl and y is an integer, e.g. 10 to 15; I

(e) or a reaction product of a long chain fatty alcohol with ethyleneoxide (10 to 15 molecules) of the formula R'o-(CHzCHzohH, in whichR isthe radicle of a long fatty alcohol, and z is an integer, e. g. 10 to15;

(,f) or a monoor di-ester of long chain fatty acids containing at least12 carbon atoms with a polyalkylene glycol of a molecular weight ofbetween 400 and 1540, such as nona-ethylene glycol monolaurate,trideca-ethylene glycol monolaurate, trideca-ethylene glycol dilaurate,the monostearic ester of Carbowax 1000 (a polyethylene glycol of anaverage molecular weight of 1000), the dipalmitic ester of Carbowax1000, the monooleic ester of Carbowax 1540 (a poly-ethyleneglycol of anaverage molecular weight of 1540), the diricinoleic ester of Carbowax1540;

(g) or a non-ionic condensation product of a long chain fatty acid, orits derivative, with at least two molecules of a hydroxylated amine.

Mixtures of two or more of these non-ionic surface active agents may beemployed; Products which contain ethylene oxide chains in theirmolecules are preferred. Water soluble resinlike products and thickeningagents, like polyvinyl alcohol, or methyl cellulose, however, aregenerally not desirable.

The ingredients described above may'be'employed in varying proportions.The amount of wax should not be substantially above 30% in the case ofparaffin wax, or 25% in the case'of animal or vegetable wax, by weightof the total composition.

The amount of amine soap may vary from about 8 parts to about 25 partsfor 100 partsof the wax. The amine and the fatty acid, from whichingredients this amine soap is made, may be used in stoichiometricproportions, or a slight accepts excess of the fatty --ac-id over theamine may "be employed. An excess of the amine over the fatty acidshould only be employed if the amine is highly volatile and might bepartially lost during themanufacture of the emulsion. Higher amounts ofthe amine soapmay be used, but this is not necessary and will detractfrom the hydrophobic properties of the materials treated withtheemulsion.

"The 'polyv'alent metal salt is .preterably used in form of the aqueoussolution. The metal Salt50111171011 TIIEYCOIlStitHtSTbEtWEGIL I0 and 30%by weight, .of the total composition. A 20% aluminum 'formate or 24%.alumimim :acetate solution may'zbe .used; :or between Band 25%, byweight, of the total composition may consist of zirconium acetatesolution of 1.238 specific gravity (containing 15% Zr'Ozper liter).

.The non-ionic surface active agent may be used from about 0.25% up to 3on an anhydrous basis, by weight of the total composition. The optimumamount will somewhat depend on the nature .of the .non-ionic agent. Somenon-ionic agents,.like ethylene oxide addition products of sorbitanmonofatty acid esters, are active at a lower concentration than others,e. g., non-ionic fatty acid-hydroxylated amine condensation products.

Higher proportions of the non-ionic agents may .be employed. The amountof non-ionic agent required to thin out and disperse a precipitatealready formed is smaller than the amount necessary to entirely preventformation of a precipitate. For most purposes, using enough nonionicagent to avoid entirely formation of a precipitate is preferred overjust adding enough to thin out and disperse the precipitate.

The wax-amine soap emulsion may be prepared by melting the amine, fattyacid, and wax together and then adding gradually the water Whilestirring and cooling. Mixing the molten wax into thehot aqueous aminesoap solution or melting wax and fatty acid together and pouring .theminto ahot mixture of water and amine are alternate procedures.

The wax-amine soap emulsion is desirably cooled to not substantiallyabove room tempera ture before it is mixed with the solution of thevpolyvalent metal salt.

The non-ionic agent may be added:

(a) To the wax-amine soap emulsion while it is molten, or

(b) To the aqueous phase before mixing, or

to) .To the wax phase before mixing, or

(d) .To the wax-amine soap emulsion while cooling, or after cooling, or

(e) To the polyvalent metal salt solution, or

(f) To the final emulsion after the polyvalent metal salt has been mixedwith the other ingredients.

It is, however, preferred to add the non-ionic agent to the wax-aminesoap emulsion during or after cooling, and before mixing with the.polyvalent metal salt solution.

It is also preferred to pour the amine soap-wax emulsion into thesolution of the polyvalent metal salt at or below room temperature, withvigorous agitation.

The final emulsion may be passed through a colloid mill or similarhomogenizing equipment, if desired. This is, however, not required sincethe emulsion is smooth and homogeneous. Other ingredients useful intreating textiles and paper may be added to improve or modify theproperties of these materials; e. 'g. materials to reducewinflammability, to :improve rmi-ldew :resistance, hand, and appearance.;Asmentioned later, these novel emulsions are compatible with :a greatnumbernf otheringredients;and,:11neXpectedly, also withsynthetimlatices.

The invention may :he Zillustrated ,byuthe .following examples, in whichparts nnean ;.parts by weight:

flazamplell An emulsion is prepared "from 20"parts -of parafiin (melting,point, 52 to 55 0;), *3 :parts of stearic acid, 1.5 parts oftriethanolaminearfdfib parts of water. The emulsion is cooledtoroomtemperature, and 20 parts ofaluminum acetate solution (241%) rare:added, with :agitation. A heavy precipitate :firstiorms, which.cdisperses, however, on continued iagitationtoiormzaheayy paste, which:cannot .be poured, and cannot be diluted with water withouttbreakdown.

To 100 parts of this ,paste, 1 .part .of monolauric acid ester of apolyethylene, glycoloflansaverage molecular weight of 6001s added, withvigorous agitation. After ashort while, the.heavy paste changes itsconsistency andforms a thin, po.urable, milky liquid, which.is.stablefonstoragezand easily dilutable with water.

Example II 22 parts of paraffin wax (melting point, :60 to 62 C.) areheated together with :3 parts of .a hydrogenated fish oil fattyacidfractionof acid value 179 (corresponding to a fatty.-acid.of:an averagechain length of 20 carbon atoms) and poured into a solution of 0.7 partof morpholine in 34.3 parts of water, with vigorous .agitation at atemperature of .between '80 and .C.

The mixture is allowed to cool withstirring. When the emulsionhasreached room temperature, a solution of .1.5 parts of mono-oleic acidester of a polyethylene glycol "of average molecular weight of 1540111122.5 "parts-of water isiadded.

Then the mixture :is poured, with :stirring, into 15 parts ofiazirconiumacetate solution ;of specific gravity 1.23.8.

The resulting emulsion is thin and monrable, and stable on storage.

Example III 25 parts of an emulsion of copolymer of 60% styrene and 40%butadiene (availableas Dow Latex 512 fromDow Chemical .Co.).arezgradually added to ,parts :of the emulsion .of Example II.

The resulting product is thin, readily dilutable with water, and stablefor a period of many months without breakdown.

Example] V 22 parts of paraffin of. melt ng 'pointi52to '55 C. and 2parts of hydrogenated fish oil fatty acid are melted together and pouredinto a boiling solution of 0.5 part of monoisopropanolamine in 35.5parts of water.

The mixture is allowed to cool to room temperature. Then 0.5 part of theethylene oxide addition product vof iso-octyl phenol, dissolved in 19.5parts of water, are added. The mixture is finally poured into 20 partsof a-20%-a1uminum formate solution.

The emulsion has a similar appearance as the emulsions described in theprevious examples.

Example V 21 parts of parafiin (melting point, 52-:to-r55" .C.) aremelted together with.-2rpartsz o'frpalmitic acid and poured into aboiling solution of 1.2 parts of triethanolamine in 35.8 parts of water,with agitation.

After cooling to room temperature, 2 parts of the coconut fatty aciddiester of a polyethylene glycol of average molecular weight 1000,dispersed in 8 parts of water, are added. This emulsion is poured into asolution of 6 parts of copper acetate and 1 part of glacial acetic acidin 19 parts of water.

This emulsion may be usedafter dilution with waterto increase the mildewresistance of textiles.

Example VI 1.9 parts of triethanolamine, 3.6 parts of stearic acid and50.5 parts of water. are heated to 100 C. 20 parts of beeswax are meltedseparately and added, with good agitation, to the boiling amine soapsolution and allowed to cool. 2 parts of the mono-myristic acid ester ofa polyethylene glycol of average molecular weight 1000, dissolved in 2parts of water, are added. The mixture is then poured into 20 parts of24% aluminum acetate solution, with stirring. A smooth emulsion isformed.

Example VII 1.4 parts of triethanolamine, 2.6 parts of hydrogenated fishoil fatty acid and 60 parts of water are heated to 100 C. 15 parts ofcarnauba wax are heated separately to 100 C. and added, with goodagitation, to the boiling soap solution. The mixture is stirred untilcool.

1 part of the ethylene oxide addition product of sorbitan monolaurate isadded, and the mixture is poured into 20 parts of a 24% aluminum acetatesolution, with stirring. A smooth emulsion is formed, easily dilutablewith water.

Example VIII yielding a smooth, pourable emulsion.

Example IX 27 parts of parafiin (melting point, 55 to 60 C.) are meltedtogether with 3.8 parts of a hydrogenated fish oil fatty acid fractionof acid value 179, and stirred into a boiling mixture of 0.9 part ofmorpholine and 44.3 parts of water.

After cooling, a dispersion of 2 parts of nonaethyleneglycol monolauratein 2 parts of water is added and the mixture is stirred into 20 parts ofa zirconium acetate solution containing 15% 2102.

Example X 20 parts of paraffin and 2 parts of candelilla wax areemulsified in a mixture of 1 part 2- methyl-2-amino-1-3-propanediol, 3parts of hydrogenated fish oil fatty acid and 40 parts of water. To thecooled emulsion a solution of 1 part of the monolauric acid ester ofpolyethylene glycol of average molecular weight of 1000 and 0.25 part ofthe coconut fatty acid Example XI 21 parts of parafiin (melting point,60 to 62 C.) are melted with 3 parts of behenic acid and stirred into aboiling mixture of 0.5 part of monoethanolamine and 35.5 parts of water.

After cooling, a dispersion of 2.5 parts of man nitan monopalmitate in17.5 parts of water is added. Then the emulsion is stirred into 20 partsof 20% aluminum formate solution.

Example XII 5 parts of the emulsion described in Example II are dilutedwith parts of water of 35 C.

A textile fabric is impregnated with this solution, squeezed to removeexcess liquid, and dried at C. The fabric shows an excellent waterrepellency. A short heat treatment, for example, at 3 minutes at C'.will improve the permanency of this effect;

Generally, the inclusion of the non-ionic agent results in quite unusualproperties. If a small amount of non-ionic surface active agents isadded to a heavy paste resulting after addition of a solution of a watersoluble polyvalent metal salt to a wax emulsion containing soap asemulsifler, the heavy paste thins out to a pourable consistency, and maybe diluted with water without breakdown.

If a small amount of said non-ionic agent is added to a soap containingwax emulsion, prior to the addition of the polyvalent metal salt, theprecipitate of the polyvalent metal-soap-wax complex will not form atall, or if it does form, it will readily disappear on stirring, forminga water-thin mixture, which is readily dilutable with water.

Moreover, such an emulsion is perfectly stable on storage. It doesneither cream, nor show any signs of breakdown, nor lose its property ofbeing readily dilutable with water, for a period of many months, orlonger. Besides, the diluted emulsion yields a superior water-repellenteffect on textiles and paper, and does not show any greasy spots.

Synthetic resin latices, prepared from vinyl acetate, or butadiene andstyrene, or butadiene and acrylonitrile, by the so-called emulsionpolymerization, may also be added to the above emulsion withoutcoagulation of the mixture. Since these latices are very sensitive topolyvalent metal ions, and usually coagulate immediately in presence ofthese ions, this behavior is quite unexpected.

The mixture of latex and the above wax emulsions may be used to impart avery desirable finish to textile materials in a one-bath procedure.

The present invention is most valuable in treating materials to renderthem water-repellent. The wax emulsions of this invention are quitedifferent from those containing glue or gelatin. Such glue or gelatinemulsions do not flow freely at the higher wax concentrations, are heavypastes, and are not readily dilutable with water before use.

The wax emulsions of the present invention, on the other hand, are thinand flowable, may readily be diluted with water to any desiredconcentration by simple mixing.

anemone Generally; in; summary, the present applicant has found thatmost satisfactory water-repellent compositions are not obtained by usingas the dispersing or emulsifying agents combinations of cationic surfaceactive agents and protein protective colloids, non-ionic surface activeagents and protein colloids and anionic surface active agentsandproteinprotective colloids since not only do they permit ready break-down ofthe wax emulsion with poor dilutability and undesirable' thickening withthe additional defect of resulting in putrefacation of the emulsion andmildew attack upon the treated cloth.

Moreover, it is not readily possible to. employ asthe. desired agentscationic or non-ionic surface active agents by themseives, since theseagents give coarse emulsions which tend to breakdown or become disruptedquite readily. The present invention is particularly directed to anemulsion in which an anionic surface active agent and a non-ionicsurface active agent excluding a cationic agent and protein protectivecolloids are employed to give a stable wax water-proofing emulsion.

Generally, the preferred anionic agent is an ethanolamine soap while thepreferred non-ionic surface active agents are alkylene oxidecondensation products containing at least 6 alkylene oxide groups whichare generally known by the trade-marks of Tweens, Igepal, Triton N. E.,Sharples Non-Ionic No. 218, Emulphcr, Peregal or Carbowax esters.

The non-ionic agents may also be anhydrides of polyhydric alcohols whichare partly esterfied such as those known as Span, or condensationproducts of alkanolamines and high molecular weight fatty acids, knownin the trade as Ninol, Ultrapon, Cerfak N-100 and Alrosol.

Generally, the compounds known as Tweens, Igepal and Carbowax 1000monolaurate are most satisfactorily employed.

Not only may the present emulsions be used for water-proofing or waterrepellent treatment, but they also may be utilized in connection withflame-proofing, finishing fabrics to give a soft or pliable hand, or toapply resin finishes thereto, as for example in connection with crushproofing or slip proofing. The emulsions of the present application mayalso be applied to leather goods, metal goods and to sheet plastics.

While there has been herein described a preferred form of the invention,it should be understood that the same may be altered in details and inrelative arrangement of parts within the scope of the appended claims.

Having now particularly described and ascertained the nature of theinvention, and in what manner the same is to be performed, what isclaimed is:

1. An aqueous emulsion of the oil-in-water type suitable forwaterproofing textiles and the like, comprising about 10 to 30% of awax, about 0.8 to 7.5% of an amine soap of a saturated fatty acid havingat least 12 carbon atoms, about 8 to 30% of a solution of a watersoluble polyvalent metal salt of an organic acid of about 4 to 15%strength (calculated as the oxide of said metal), about 0.25 to 3% of awater soluble non-ionic surface active agent, the balance being watersaid polyvalent metal salt being selected from the group consisting ofaluminum zirconium and copper.

2. An aqueous emulsion of the oil-in-water type suitable forwaterproofing textiles and the like, as described in claim 1, in whichthe wax I0 is lparafiin wax, and-iiniwhich:thenoneionic agent contains.a. high molecular weight polyoxy alkylene ether containing at: least:five recurring alkylene oxide: units said. polyvalent. metal: salt beingselected from the group consisting: of aluminum zirconium and copper.

3. A textile treating. aqueous= waxemulsion: of the oil in watertypeacontaininga water-soluble soap and a waten-solublezpolyvalent-zheavyzmetal salt without mutual inter-precipitation. concentrated anddiluted: form and upon. storage, said emulsion including'aawax, anzaminesoapof a high molecular weight fatty acid, a Water soluble polyvalentmetal saltzofian organic acid and arsufiicientquantitp of: a,watersoluble non-ionic surface active: agent; to; preventsaidiinter-precipitation said polyvalent metal salt being selected from thegroup consisting of aluminum zirconium and copper.

4. A textile treating aqueous wax emulsion of the oil in water typecontaining a water-soluble soap and a water-soluble polyvalent heavymetal salt without mutual inter-precipitation in concentrated anddiluted form and upon storage, said emulsion including parafiin,morpholine salt of the fatty acids of hydrogenated fish oil and aluminumacetate and a sufiicient quantity of a water soluble non-ionic surfaceactive agent to prevent said inter-precipitation.

5. A textile treating aqueous wax emulsion of the oil in water typecontaining a water-soluble soap and a water-soluble polyvalent heavymetal salt without mutual inter-precipitation in concentrated anddiluted form and upon storage, said emulsion including parafiin,morpholine salt of the fatty acids of hydrogenated fish oil andzirconium acetate and a sufiicient quantity of a water soluble non-ionicsurface active agent to prevent said inter-precipitation.

6. A textile treating aqueous wax emulsion of the oil in water typecontaining a water-soluble soap and a water-soluble polyvalent heavymetal salt without mutual inter-precipitation in concentrated anddiluted form and upon storage, said emulsion including a wax, an aminesoap of a high molecular weight fatty acid, a water soluble polyvalentmetal salt of an organic acid and a sufficient quantity of a non-ionicsurface active agent to prevent said inter-precipitation, said non-ionicsurface agent being an alkylene oxide condensation product andcontaining at least five recurring ethylene oxide units in an etherlikelinkage.

'7. A thin pourable water repellant concentrated emulsion for textilesand the like containing a dispersion of about 10 to 30% of a waxtogether with a water-soluble soap, a water soluble polyvalent metalsalt of an organic acid and a synthetic water soluble non-ionic surfaceactive agent, said emulsion being stable in storage and readilydilutable with water without precipitation said polyvalent metal saltbeing selected from the group consisting of aluminum zirconium andcopper.

8. The emulsion of claim 7, in which the soap is an amine soap.

9. The emulsion of claim 7, in which the soap is a morpholine compoundof saturated high molecular weight fatty acid.

10. The emulsion of claim 7, in which the soap is an ethanolaminecompound of saturated high molecular weight fatty acid.

11. The emulsion of claim 7, in which the wax is parafiin.

11 12. The emulsion of claim 7, in which the polyvalent metal salt iszirconium acetate.

13. The emulsion of claim 7, in which the polyvalent metal salt isaluminum acetate.

. 14. The emulsion of claim 7, in which the polyvalent metal salt isaluminum formate.

15. An aqueous emulsion of the oil-in-water type suitable forwaterproofing textiles and the like, as described in claim 1, in whichthe wax is paraflin wax and in which the non-ionic agent is acondensation product of a long chain fatty acid with at least 2molecules of a hydroxylated amine.

16. An aqueous emulsion of the oil-in-water type suitable forwaterproofing textiles and the like, as described in claim 15, in whichthe long 12 chain fatty acid is coconut fatty acid, and the amine isdiethanolamine.

HANS G. FIGDOR.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,015,865 Muller Oct. 1, 1935 2,133,480 Schoeller et a1 Oct.18, 1938 2,206,090 Haggenmacher July 2, 1940 2,269,529 Goldsmith Jan.13, 1942 2,328,431 Doser et a1. Aug. 31, 1943 2,369,992 Treaey Feb. 20,1945 2,447,475 Kaberg et al Aug. 17, 1948 2,456,595 Rood Dec. 14, 1948

1. AN AQUEOUS EMULSION OF THE OIL-IN-WATER TYPE SUITABLE FORWATERPROFFING TEXTILES AND THE LIKE, COMPRISING ABOUT 10 TO 30% OF AWAX, ABOUT 0.8 TO 7.5% OF AN AMINE SOAP OF A SATURATED FATTY ACID HAVINGAT LEAST 12 CARBON ATOMS, ABOUT 8 TO 30% OF A SOLUTION OF A WATERSOLUBLE POLYVALENT METAL SALT OF AN ORGANIC ACID OF ABOUT 4 TO 15%STRENGTH (CALCULATED AS THE OXIDE OF SAID METAL), ABOUT 0.25 TO 3% OF AWATER SOLUBLE NON-IONIC SURFACE ACTIVE AGENT, THE BALANCE BEING WATERSAID POLYVALENT METAL SALT BEING SELECTED FROM THE GROUP CONSISTING OFALUMINUM ZIRCONIUM AND COPPER.